Yanli dielectric materials and capacitor thereof

ABSTRACT

A composite polymeric material includes one or more repeating backbone units; one or more polarizable units incorporated into or connected to one or more of the one or more repeating backbone units; and one or more resistive tails connected to one or more of the repeating backbone units or to the one or more polarizable units as a side chain on the polarizable unit, on a hydrocarbon chain linking a polarizable unit to a backbone unit, or directly attached to a backbone unit. The composite polymeric material may be used to form a metadielectric, which may be sandwiched between to electrodes to form a metacapacitor.

CLAIM OF PRIORITY

This application is a continuation-in-part of U.S. patent applicationSer. No. 15/449,587, filed Mar. 3, 2017, the entire contents of whichare incorporated herein by reference and U.S. patent application Ser.No. 15/449,524 filed Mar. 3, 2017, the entire contents of which arehereby incorporated herein by reference in their entirety.

FIELD OF THE INVENTION

The present disclosure relates generally to passive components ofelectrical circuits and more particularly to a composite organiccompound and capacitor based on this material and intended for energystorage. A capacitor is an energy storage device that stores an appliedelectrical charge for a period of time and then discharges it. It ischarged by applying a voltage across two electrodes and discharged byshorting the two electrodes. A voltage is maintained until dischargeeven when the charging source is removed. A capacitor blocks the flow ofdirect current and permits the flow of alternating current. The energydensity of a capacitor is usually less than for a battery, but the poweroutput of a capacitor is usually higher than for a battery. Capacitorsare often used for various purposes including timing, power supplysmoothing, coupling, filtering, tuning and energy storage. Batteries andcapacitors are often used in tandem such as in a camera with a flash.The battery charges the capacitor that then provides the high powerneeded for a flash. The same idea works in electric and hybrid vehicleswhere batteries provide energy and capacitors provide power for startingand acceleration.

BACKGROUND

A capacitor is a passive electronic component that is used to storeenergy in the form of an electrostatic field, and comprises a pair ofelectrodes separated by a dielectric layer. When a potential differenceexists between the two electrodes, an electric field is present in thedielectric layer. An ideal capacitor is characterized by a singleconstant value of capacitance, which is a ratio of the electric chargeon each electrode to the potential difference between them. For highvoltage applications, much larger capacitors have to be used.

One important characteristic of a dielectric material is its breakdownfield. This corresponds to the value of electric field strength at whichthe material suffers a catastrophic failure and conducts electricitybetween the electrodes. For most capacitor geometries, the electricfield in the dielectric can be approximated by the voltage between thetwo electrodes divided by the spacing between the electrodes, which isusually the thickness of the dielectric layer. Since the thickness isusually constant it is more common to refer to a breakdown voltage,rather than a breakdown field. There are a number of factors that candramatically reduce the breakdown voltage. In particular, the geometryof the conductive electrodes is important factor affecting breakdownvoltage for capacitor applications. In particular, sharp edges or pointshugely increase the electric field strength locally and can lead to alocal breakdown. Once a local breakdown starts at any point, thebreakdown will quickly “trace” through the dielectric layer until itreaches the opposite electrode and causes a short circuit.

Breakdown of the dielectric layer usually occurs as follows. Intensityof an electric field becomes high enough to “pull” electrons from atomsof the dielectric material and makes them conduct an electric currentfrom one electrode to another. Presence of impurities in the dielectricor imperfections of the dielectric structure can result in an avalanchebreakdown as observed in semiconductor devices.

Another important characteristic of a dielectric material is itsdielectric permittivity. Different types of dielectric materials areused for capacitors and include ceramics, polymer film, paper, andelectrolytic capacitors of different kinds. The most widely used polymerfilm materials are polypropylene and polyester. Increasing dielectricpermittivity while maintaining high resistivity allows for increasingvolumetric energy density, which makes it an important technical task.

One method for creating dielectrics with high permittivity is to usehighly polarizable materials which when placed between two electrodesand subjected to an electric field can more easily absorb more electronsdue to polarized ends of the molecule orienting toward oppositelycharged electrodes. U.S. patent application Ser. No. 15/449,587demonstrates a method of incorporating highly polarizable molecules intoan oligomer to create such a dielectric material and is herebyincorporated in its entirety by reference.

The article “Synthesis and spectroscopic characterization of analkoxysilane dye containing C. I. Disperse Red 1” (Yuanjing Cui, MinquanWang, Lujian Chen, Guodong Qian, Dyes and Pigments, 62 (2004) pp. 43-47)describe the synthesis of an alkoxysilane dye (ICTES-DR1) which wascopolymerized by sol-gel processing to yield organic-inorganic hybridmaterials for use as second-order nonlinear optical (NLO) effect. C. I.Disperse Red 1 (DR1) was attached to Si atoms by a carbamate linkage toprovide the functionalized silane via the nucleophilic addition reactionof 3-isocyanatopropyl triethoxysilane (ICTES) with DR1 usingtriethylamine as catalyst. The authors found that triethylamine anddibutyltin dilaurate were almost equally effective as catalysts. Thephysical properties and structure of ICTES-DR1 were characterized usingelemental analysis, mass spectra, 1H-NMR, FTIR, UV-visible spectra anddifferential scanning calorimetry (DSC). ICTES-DR1 displays excellentsolubility in common organic solvents.

Second-order nonlinear optical (NLO) effects of organic molecules havebeen extensively investigated for their advantages over inorganiccrystals. Properties studied, for example, include their large opticalnon-linearity, ultra-fast response speed, high damage thresholds and lowabsorption loss, etc. Particularly, organic thin films with excellentoptical properties have tremendous potential in integrated optics suchas optical switching, data manipulation and information processing.Among organic NLO molecules, azo-dye chromophores have been a specialinterest to many investigators because of their relatively largemolecular hyper-polarizability (b) due to delocalization of thep-electronic clouds. They were most frequently either incorporated as aguest in the polymeric matrix (guest-host polymers) or grafted into thepolymeric matrix (functionalized polymers) over the past decade.

Chromophoric orientation is obtained by applying a static electric fieldor by optical poling. Whatever the poling process, poled-order decay isan irreversible process which tends to annihilate the NLO response ofthe materials and this process is accelerated at higher temperature. Fordevice applications, the most probable candidate must exhibit inherentproperties that include: (i) high thermal stability to withstand heatingduring poling; (ii) high glass transition temperature (T_(g)) to lockthe chromophores in their acentric order after poling.

Most of the polymers, however, have either low T_(g) or poor thermalstability which makes them unsuitable for direct use. To overcome theseproblems, one attractive approach is incorporating the nonlinear opticalactive chromophore into a polymerizable silane by covalent bond to yieldan alkoxysilane dye which can be copolymerized via sol-gel processing toform organic-inorganic hybrid materials. The hydrolysis and condensationof functionalized silicon alkoxydes can yield a rigid amorphousthree-dimensional network which leads to slower relaxation of NLOchromophores. Therefore, sol-gel hybrid nonlinear optical materials havereceived significant attention and exhibited the desired properties. Inthis strategy, the design and synthesis of new network-formingalkoxysilane dye are of paramount importance.

In the article “Design and Characterization of Molecular NonlinearOptical Switches” (Frederic Castet et. al., ACCOUNTS OF CHEMICALRESEARCH, pp. 2656-2665, (2013), Vol. 46, No. 11), Castet et. al.illustrate the similarities of the experimental and theoretical tools todesign and characterize highly efficient NLO switches but also thedifficulties in comparing them. After providing a critical overview ofthe different theoretical approaches used for evaluating the firsthyperpolarizabilities, Castet et. al. reported two case studies in whichtheoretical simulations have provided guidelines to design NLO switcheswith improved efficiencies. The first example presents the jointtheoretical/experimental characterization of a new family ofmulti-addressable NLO switches based on benzazolo-oxazolidinederivatives. The second focuses on the photoinduced commutation inmerocyanine-spiropyran systems, where the significant NLO contrast couldbe exploited for metal cation identification in a new generation ofmultiusage sensing devices. Finally, Castet et. al. illustrated theimpact of environment on the NLO switching properties, with examplesbased on the keto-enol equilibrium in aniline derivatives. Through theserepresentative examples, Castet et. al. demonstrated that the rationaldesign of molecular NLO switches, which combines experimental andtheoretical approaches, has reached maturity. Future challenges consistin extending the investigated objects to supramolecular architecturesinvolving several NLO-responsive units, in order to exploit theircooperative effects for enhancing the NLO responses and contrasts.

Two copolymers of 3-alkylthiophene (alkyl=hexyl, octyl) and a thiophenefunctionalized with Disperse Red 19 (TDR19) as chromophore side chainwere synthesized by oxidative polymerization by Marilú Chávez-Castilloet. al. (“Third-Order Nonlinear Optical Behavior of Novel PolythiopheneDerivatives Functionalized with Disperse Red 19 Chromophore”, HindawiPublishing Corporation International Journal of Polymer Science, Volume2015, Article ID 219361, 10 pages,http://dx.doi.org/10.1155/2015/219361). The synthetic procedure was easyto perform, cost-effective, and highly versatile. The molecularstructure, molecular weight distribution, film morphology, and opticaland thermal properties of these polythiophene derivatives weredetermined by NMR, FT-IR, UV-Vis GPC, DSC-TGA, and AFM. The third-ordernonlinear optical response of these materials was performed withnanosecond and femtosecond laser pulses by using the third-harmonicgeneration (THG) and Z-scan techniques at infrared wavelengths of 1300and 800 nm, respectively. From these experiments, it was observed thatalthough the TRD19 incorporation into the side chain of the copolymerswas lower than 5%, it was sufficient to increase their nonlinearresponse in solid state. For instance, the third-order nonlinearelectric susceptibility of solid thin films made of these copolymersexhibited an increment of nearly 60% when TDR19 incorporation increasedfrom 3% to 5%. In solution, the copolymers exhibited similar two-photonabsorption cross sections σ_(2PA) with a maximum value of 8545 GM and233 GM (1 GM=10⁻⁵⁰ cm⁴ s) per repeated monomeric unit.

The theory of molecular nonlinear optics based on the sum-over-states(SOS) model was reviewed by Mark G. Kuzyk et. al. (“Theory of MolecularNonlinear Optics”, Advances in Optics and Photonics 5, 4-82 (2013) doi:10.1364/AOP .5.000004). The interaction of radiation with a singlewtp-isolated molecule was treated by first-order perturbation theory,and expressions were derived for the linear (α_(ij)) polarizability andnonlinear (β_(ijk), γ_(ijkl)) molecular hyperpolarizabilities in termsof the properties of the molecular states and the electric dipoletransition moments for light-induced transitions between them. Scaleinvariance was used to estimate fundamental limits for thesepolarizabilities. The crucial role of the spatial symmetry of both thesingle molecules and their ordering in dense media, and the transitionfrom the single molecule to the dense medium case (susceptibilities χ⁽¹⁾_(ij), χ⁽²⁾ _(ijk), χ⁽³⁾ _(ijkl)), is discussed. For example, forβ_(ijk), symmetry determines whether a molecule can support second-ordernonlinear processes or not. For non-centrosymmetric molecules, examplesof the frequency dispersion based on a two-level model (ground state andone excited state) are the simplest possible for β_(ijk) and examples ofthe resulting frequency dispersion were given. The third-ordersusceptibility is too complicated to yield simple results in terms ofsymmetry properties. It will be shown that whereas a two-level modelsuffices for non-centrosymmetric molecules, symmetric molecules requirea minimum of three levels in order to describe effects such astwo-photon absorption. The frequency dispersion of the third-ordersusceptibility will be shown and the importance of one and two-photontransitions will be discussed.

The promising class of (polypyridine-ruthenium)-nitrosyl complexescapable of high yield Ru—NO/Ru—ON isomerization has been targeted as apotential molecular device for the achievement of complete NLO switchesin the solid state by Joelle Akl, Chelmia Billot et. al. (“Molecularmaterials for switchable nonlinear optics in the solid state, based onruthenium-nitrosyl complexes”, New J. Chem., 2013, 37, 3518-3527). Acomputational investigation conducted at the PBE0/6-31+G** DFT level forbenchmark systems of general formula [R-terpyridine-Ru^(II)Cl₂(NO)](PF₆)(R being a substituent with various donating or withdrawingcapabilities) lead to the suggestion that an isomerization could producea convincing NLO switch (large value of the β_(ON)/β_(OFF) ratio) for Rsubstituents of weak donating capabilities. Four new molecules wereobtained in order to test the synthetic feasibility of this class ofmaterials with R=4′-p-bromophenyl, 4′-p-methoxyphenyl,4′-p-diethylaminophenyl, and 4′-p-nitrophenyl. The different cis-(Cl,Cl)and trans-(Cl,Cl) isomers can be separated by HPLC, and identified byNMR and X-ray crystallographic studies.

Single crystals of doped aniline oligomers can be produced via a simplesolution-based self-assembly method (see Yue Wang et. al.,“Morphological and Dimensional Control via Hierarchical Assembly ofDoped Oligoaniline Single Crystals”, J. Am. Chem. Soc. 2012, v. 134, pp.9251-9262). Detailed mechanistic studies reveal that crystals ofdifferent morphologies and dimensions can be produced by a “bottom-up”hierarchical assembly where structures such as one-dimensional (1-D)nanofibers can be aggregated into higher order architectures. A largevariety of crystalline nanostructures including 1-D nanofibers andnanowires, 2-D nanoribbons and nanosheets, 3-D nanoplates, stackedsheets, nanoflowers, porous networks, hollow spheres, and twisted coilscan be obtained by controlling the nucleation of the crystals and thenon-covalent interactions between the doped oligomers. These nanoscalecrystals exhibit enhanced conductivity compared to their bulkcounterparts as well as interesting structure-property relationshipssuch as shape-dependent crystallinity. Further, the morphology anddimension of these structures can be largely rationalized and predictedby monitoring molecule-solvent interactions via absorption studies.Using doped tetraaniline as a model system, the results and strategiespresented by Yue Wang et. al. provide insight into the general scheme ofshape and size control for organic materials.

Hu Kang et. al. detail the synthesis and chemical/physicalcharacterization of a series of unconventional twisted π-electron systemelectro-optic (EO) chromophores (“Ultralarge Hyperpolarizability Twistedπ-Electron System Electro-Optic Chromophores: Synthesis, Solid-State andSolution-Phase Structural Characteristics, Electronic Structures, Linearand Nonlinear Optical Properties, and Computational Studies”, J. AM.CHEM. SOC. 2007, vol. 129, pp. 3267-3286). Crystallographic analysis ofthese chromophores reveals large ring-ring dihedral twist angles(80-89°) and a highly charge-separated zwitterionic structure dominatingthe ground state. NOE NMR measurements of the twist angle in solutionconfirm that the solid-state twisting persists essentially unchanged insolution. Optical, IR, and NMR spectroscopic studies in both thesolution phase and solid state further substantiate that the solid-statestructural characteristics persist in solution. The aggregation of thesehighly polar zwitterions is investigated using several experimentaltechniques, including concentration-dependent optical and fluorescencespectroscopy and pulsed field gradient spin-echo (PGSE) NMR spectroscopyin combination with solid-state data. These studies reveal clearevidence of the formation of centrosymmetric aggregates in concentratedsolutions and in the solid state and provide quantitative information onthe extent of aggregation. Solution-phase DC electric-field-inducedsecond-harmonic generation (EFISH) measurements reveal unprecedentedhyperpolarizabilities (nonresonant μβ as high as −488,000×10⁻⁴⁸ esu at1907 nm). Incorporation of these chromophores into guest-host poledpolyvinylphenol films provides very large electro-optic coefficients(r₃₃) of ˜330 μm/V at 1310 nm. The aggregation and structure-propertyeffects on the observed linear/nonlinear optical properties werediscussed. High-level computations based on state-averaged completeactive space self-consistent field (SA-CASSCF) methods provide a newrationale for these exceptional hyperpolarizabilities and demonstratesignificant solvation effects on hyperpolarizabilities, in goodagreement with experiment. As such, this work suggests new paradigms formolecular hyperpolarizabilities and electro-optics.

U.S. Pat. No. 5,395,556 (Tricyanovinyl Substitution Process for NLOPolymers) demonstrate NLO effect of polymers that specifies a lowdielectric constant. U.S. patent application Ser. No. 11/428,395 (HighDielectric, Non-Linear Capacitor) develops high dielectric materialswith non-linear effects. It appears to be an advance in the art toachieve non-linear effects through supramolecular polarizable structuresthat are insulated from each other that include doping properties in theconnecting insulating or resistive elements to the composite organiccompound. It further appears to be an advance in the art to combinecomposite organic compounds with non-linear effects that form orderedstructures in a film and are insulated from each other and do not relyon forming self-assembled monolayers on a substrate electrode.Additionally, it appears to be an advance to achieve high dielectricnon-linear capacitors in which a dielectric is comprised ofsupramolecular polarizable structures and wherein the supramolecularpolarizable structures are arranged perpendicular to electrodes and aredispersed in a dielectric layer more or less stochastically,semi-ordered, or crystalline. Semi-ordered and stochastically disperseddielectric layers comprised of said composite organic compounds have, insome instances, more favorable mechanical properties over purely crystaldielectrics.

The production and use of oligomers of azo-dye chromophores withresistive tails is described in U.S. Patent Application 62/318,134 whichis hereby incorporated in its entirety by reference.

Capacitors as energy storage device have well-known advantages versuselectrochemical energy storage, e.g. a battery. Compared to batteries,capacitors are able to store energy with very high power density, i.e.charge/recharge rates, have long shelf life with little degradation, andcan be charged and discharged (cycled) hundreds of thousands or millionsof times. However, capacitors often do not store energy in small volumeor weight compared with batteries, or at low energy storage cost, whichmakes capacitors impractical for some applications, for example electricvehicles. Accordingly, it may be an advance in energy storage technologyto provide capacitors of higher volumetric and mass energy storagedensity and lower cost.

A need exists to improve the energy density of film capacitors whilemaintaining the existing power output and durability or lifetime. Thereexists a further need to provide a capacitor featuring a high dielectricconstant sustainable to high direct current (DC) voltages where thecapacitance is voltage dependent. Such a capacitor is the subject of thepresent disclosure. The capacitor of the present disclosure builds onpast work on non-linear optical chromophores and non-linear capacitorscomprising said chromophores.

In high frequency applications, it is often important that thecapacitors used do not have high dielectric losses. In the case offerroelectric ceramic capacitors with a high dielectric constant, thepresence of domain boundaries and electrostriction provide lossmechanisms that are significant. In contrast, the high dielectricmechanism disclosed in this disclosure involves the movement of anelectron in a long molecule and its fixed donor.

A second very useful property of the type of capacitor disclosed in thedisclosure is its non-linearity. In many applications, it is desirableto have a voltage sensitive capacitance to tune circuits and adjustfilters. The disclosed capacitors have such a property; as the mobileelectron moves to the far end of the composite organic compounds as thevoltage increases, its motion is stopped so that with additional voltagelittle change in position occurs.

A third useful property of the type of capacitor disclosed in thedisclosure is its resistivity due to resistive tails covalently bondedto the composite organic compound or in a polymer. In many instances,electron mobility is hindered by a matrix of resistive materials. Acomposite of a non-linear polarizable compound and electricallyresistive tails introduces order to a film of consisting of a compositeorganic compound or a polymer which can enhance the energy density ofcapacitors. This is achieved by increasing the density of polarizationunits by also limiting mobility of pi or ionic electrons to thechromophores and/or reducing electron tunneling. Ordered resistive tailscan further enhance the energy density of capacitors by improvingpacking, increasing internal film organization, increasingcrystallinity, reducing voids, or any combination thereof, which therebyincreases film resistivity, film dielectric constant, breakdown voltage,or any combination thereof.

In one example, rather than using alkyl chains for the resistive tails,rigid resistive tails can be used to introduce some order to the overallmaterial by preventing the presence of voids due to coiling of alkylchains. This is described in greater detail in U.S. patent applicationSer. No. 15/163,595, which is incorporated herein in its entirety byreference.

The resistive tails, ordered or disorder, may also crosslink to furtherenhance the structure of the dielectric film which can reduce localizedfilm defects and enhance the film's breakdown voltage or breakdownfield. Further, a polymer of a composite non-linear polarizable compoundand electrically resistive chain may crosslink inter- and/or intrapolymer backbones to enhance the dielectric film structure, which canreduce localized film defects and enhance the film's breakdown voltageor breakdown field. Further, ordered resistive tails can improvesolubility of the composite compound in organic solvents. Still further,the resistive tails can act to hinder electro-polar interactions betweensupramolecular structures formed from pi-pi stacking of the optionallyattached polycyclic conjugated molecule. Even further, the resistivetails can act to hinder electro-polar interaction between repeat unitsof a polymer consisting of non-linear polarizable compounds.

A co-polymer consisting of a monomer with a non-linear polarizablecompound and a monomer with a resistive tail can be used to introducesome order to dielectric films consisting of said co-polymer due to theresistive tails and non-linear polarizable compounds forming polar,pi-pi, van der Waals interaction, or any combination thereof. Further, ahomo-polymer consisting of a single monomer comprised of both anon-linear polarizable compound and at least one resistive tailintroduces greater order to a dielectric film consisting saidhomo-polymer. Still further, a co-polymer or homo-polymer backbone canbe selected for mechanical rigidity, which can increase order of adielectric film consisting of one or more said polymers.

A fourth very useful property of the type of capacitor disclosed in thedisclosure is enhancing the non-linear response of the chromophores byusing non-ionic dopant groups to change electron density of thechromophores. Manipulation of the electron density of the chromophorescan significantly increase the non-linear response which is useful forincreasing the polarizability and the type of dopant groups onchromophores is also important to achieving enhanced non-linearpolarization versus a neutral or deleterious effect on the non-linearityof the chromophore.

A fifth very useful property of the type of capacitor disclosed in thedisclosure is enhancing the non-linear response of the chromophores byusing non-ionic dopant connecting groups or polymer backbone unitsconsisting of a heteroatom connected to or in conjugation with thechromophore to change electron density of the chromophores. Manipulationof the electron density of the chromophores can significantly increasethe non-linear response which is useful for increasing the polarizationof the capacitor and thus energy density of said capacitor. However,placement and type of dopant connecting groups on chromophores is alsoimportant to achieving enhanced non-linear polarization versus a neutralor deleterious effect on the non-linearity of the chromophore.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 shows a metacapacitor with two electrodes and a metadielectricaccording to aspects of the present disclosure.

FIG. 2A shows a formation of two metal strips on top and bottom surfacesof the plastic layer for a coiled metacapacitor according to an aspectof the present disclosure.

FIG. 2B shows a winding of the multilayered tape for a coiledmetacapacitor according to an aspect of the present disclosure.

FIG. 3 shows a coiled film metacapacitor according to an aspect of thepresent disclosure.

FIG. 4A depicts a graph of linear polarizability α versus number ofphenyl rings p in a composite polymer according to an aspect of thepresent disclosure.

FIG. 4B depicts a graph of nonlinear polarizability β versus number ofphenyl rings p in a composite polymer according to an aspect of thepresent disclosure.

FIG. 5 illustrates an example of the chemical structure of a YanLimaterial as a monomer of a polymer according to an aspect of the presentdisclosure.

SUMMARY

Aspects of the present disclosure include a class of materials referredto herein as YanLi materials and YanLi polymers. In general, a YanLipolymer is a composite oligomeric material comprised of monomers thathave polarizable and insulating components. The monomers may include apolarizable unit having a non-linear polarizable core that includes aconjugated ring system and at least one dopant group. The monomers alsoinclude an insulating tail as a side chain on the polarizable unit, onthe handle linking a polarizable unit to the monomer backbone, ordirectly attached to the backbone. In some embodiments, a YanLi polymermay be a co-polymer wherein one monomer unit includes an insulating tailand a second monomer unit includes a polarizable unit having anon-linear polarizable core that includes a conjugated ring system andat least one dopant group. In some embodiments, the polarizable unit maybe partially or fully incorporated into the monomer backbone.Additionally, the polarizable unit may be partially or fullyincorporated into the monomer backbone.

A particular subclass of YanLi materials are referred to herein as YanLidielectrics, which are materials of one or more YanLi polymers, of oneor more YanLi oligomer, or any combination therein.

One aspect of the present disclosure is to provide a capacitor with ahigh power output. A further aspect of the present disclosure is toprovide a capacitor featuring a high dielectric constant sustainable tohigh voltage. Another aspect of the present disclosure is to provide acapacitor with a high energy density. A still further aspect of thepresent disclosure is to provide a capacitor featuring voltage dependentcapacitance. In yet another aspect of the present disclosure, a methodto make such a capacitor is provided.

The capacitor, in its simplest form, comprises a first electrode, asecond electrode and a composite oligomer, comprising ordered resistivetails and polarizable units (i.e. chromophore side chains), between thefirst electrode and the second electrode. The polarizable units on theoligomer in some instances may be chromophore side chains that havedopant groups which can be independently selected from electron acceptorand/or electron donor groups separated by a conjugated ring system withor without a conjugated bridge. The conjugated bridge comprises one ormore double bonds that alternate with single bonds in an unsaturatedcompound. Among the many elements that may be present in the doublebond, carbon, nitrogen, oxygen and sulfur are the most preferredheteroatoms. Alternatively, the conjugated bridge may comprise one ormore triple bonds that alternate with single bonds in an unsaturatedcompound. Among the elements that may be present in the triple bond,carbon is the most preferred heteroatom. The π electrons in theconjugated ring system are delocalized across the length of thechromophore. Among the many types of resistive tails that may be presentin the composite monomer, alkyl chains, branched alkyl chains,fluorinated alkyl chains, branched flouroalkyl chains, poly(methylmethacrylate) chains are examples and are preferentially positioned onthe terminal aromatic rings of a chromophore. In some embodiments, theresistive tails are positioned on side or lateral positions of thepolarizable unit or fragment of the composite organic compound.Additionally, in some embodiments, the resistive tails may be positionedon both the terminal aromatic rings and lateral or side positions ofnon-terminal aromatic rings of a chromophore. When a bias is appliedacross the first and second electrodes, the composite oligomer becomesmore or less polarized with electron density moving to compensate thefield induced by the applied bias. When the bias is removed, theoriginal charge distribution is restored. In some embodiments, thecapacitor comprises a plurality of YanLi oligomers (varying in lengthand/or type of monomer units) as a structured dielectric film withlamella or micelle structures. YanLi oligomers (typically less than 100monomer units long) may be YanLi polymers (typically greater than 100monomer units long).

Note on Nomenclature

The terms oligomer and polymer are sometimes used interchangeably.However, oligomer is more commonly used to describe a specificembodiment of a polymer, a polymer complex with short backbone length(low molecular weight), or a specific portion of a complex molecule ormotif (e.g., chromophore side chains or alkyl side chain).

DETAILED DESCRIPTION

According to aspects of the present disclosure an energy storage device,such as a capacitor, may include a composite polymeric material of anyof the types described herein sandwiched between first and secondelectrodes. The electrodes may be made conductors or semiconductors.Conductors include, but are not limited to, metals, conducting polymers,carbon nano-materials, and graphite including graphene sheets.Semiconductors include, but are not limited to, silicon, germanium,silicon carbide, gallium arsenide and selenium. The electrode may or maynot be formed on a support layer. Flat layers may include, but are notlimited to, glass, plastic, silicon, and metal surfaces.

Aspects of the present disclosure include composite polymeric materialsof the following general formula:

wherein D is

N, or a hydrocarbon chain, wherein R^(1a), R^(1b), R^(2a), R^(2b),R^(2c), R^(2d), R^(3a), R^(3b), R^(4a), R^(4b), R^(4c), R^(4d), R^(5a),R^(5b), R^(5c), R^(5d) are independently selected from —H, —OH, -Ak,-Ak-X_(l), -OAk, or -OAk-X_(l), L₂ is a heteroatom bridge in conjugationwith the ring system containing R^(2a), R^(2b), R^(2c), R^(2d), Q¹, Q²,Q³, Q⁴, Q⁵; wherein R^(2a), R^(2b), R^(2c), R^(2d), Q¹, Q², Q³, Q⁴, Q⁵are each independently selected from —H and any electron withdrawing orelectron donating group; wherein Ak is alkyl, X is any halogen, n is0-150, m is 1-300, l is 1-51, o is 0-10, p is 0-1 when o is less than orequal to one and 1 when o is greater than 1, wherein R^(1a) or R^(1b) isan insulating resistive tail or both R^(1a) and R^(2a) are insulatingresistive tails.

In some implementations of composite polymeric materials of the abovegeneral formula, the value of n may be equal to or greater than 1.

In some implementations of composite polymeric materials of the abovegeneral formula, the value of n may be equal to zero. In suchimplementations, R^(1a), R^(1b), R^(3a) or R^(3b) may possesses at least7 carbon atoms.

In some implementations of composite polymeric materials of the abovegeneral formula, R^(1a), R^(1b), R^(3a), and R^(3b) may be insulatingresistive tails are independently selected from the group consisting ofsaturated hydrocarbon, saturated halogenated hydrocarbon, partiallyhalogenated hydrocarbon, aryl chain, and cycloalkyl, and X—RR′R″;wherein X is selected from C, O, N, and S, and R, R′, and R″ areindependently selected from H and C₅₋₅₀, wherein one or more of R, R′,and R″ is C₅₋₅₀. As used in the present disclosure, the notation C₅₋₅₀means a chain of 5 to 50 carbon atoms. In such implementations a chainmay be monounsaturated or partially unsaturated, yet the unsaturatedbonds are not conjugated. In such implementations all insulatingresistive tails may be selected independently from the group consistingof non-aromatic carbocycles and non-aromatic heterocycles.

In some implementations of composite polymeric materials of the abovegeneral formula, all insulating resistive tails may be rigid.

In some implementations of composite polymeric materials of the abovegeneral formula, Q₁, Q₂, Q₃, Q₄ and Q₅ may each be independentlyselected from —NO₂, —NH₃ ⁺ and 13 NRR′R″⁺ (quaternary nitrogen salts)with counterion Cl⁻ or Br⁻, —CHO (aldehyde), —CRO (keto group), —SO₃H(sulfonic acids), —SO₃R (sulfonates), SO₂NH₂ (sulfonamides), —COOH(carboxylic acid), —COOR (esters, from carboxylic acid side), —COCl(carboxylic acid chlorides), —CONH₂ (amides, from carboxylic acid side),—CF₃, —CCl₃, —CN, —⁻ (phenoxides) with counter ion Na⁺ or K⁺, —NH₂,—NHR, —NR₂, —OH, OR (ethers), —NHCOR (amides, from amine side), —OCOR(esters, from alcohol side), alkyls, —C₆H₅, vinyls, wherein R and R′ andR″ are radicals selected from the list comprising hydrogen, alkyl(methyl, ethyl, isopropyl, tert-butyl, neopentyl, cyclohexyl etc.),allyl (—CH2-CH═CH2), benzyl (—CH2C6H5) groups, phenyl (+substitutedphenyl) and other aryl (aromatic) groups. In some such implementations,one or more of Q¹, Q², Q³, Q⁴, and Q⁵ may be —NO₂.

In some implementations of composite polymeric materials of the abovegeneral formula, D may be a hydrocarbon chain that is interrupted byheteroatoms at the point of backbone attachment and side chainattachment.

In some implementations of composite polymeric materials of the abovegeneral formula, L₂ may be an azo-bridge or —N═N—, an alkene bridge or—HC═CH—, and alkyne bridge or —C≡C—.

In some implementations of composite polymeric materials of the abovegeneral formula, the composite polymeric material may have any ofstructures 1 to 20:

wherein n ranges from 0-150 and m ranges from 1-300. Additionally, therepeat units of co-polymer variants repeat randomly, or more-or-lessone-to-one in succession.

In addition, aspects of the present disclosure include compositepolymeric materials of the following general formula:

In the above general formula [M1] is:

R^(1a), R^(1b), R^(2a), R^(2b), R^(2c), R^(2d), R^(4a), R^(4b), R^(4c),R^(4d), R^(5a), R^(5b), R^(5c), R^(5d) are independently selected from—H, —OH, -Ak, -Ak-X_(l), -OAk, or -OAk-X_(l), L₂ is a heteroatom bridgein conjugation with the ring system containing R^(2a), R^(2b), R^(2c),R^(2d), Q¹, Q², Q³, Q⁴, Q⁵; wherein R^(2a), R^(2b), R^(2c), R^(2d), Q¹,Q², Q³, Q⁴, Q⁵ are each independently selected from —H and any electronwithdrawing or electron donating group, wherein D is a hydrocarbonchain, wherein Ak is alkyl, X is any halogen, m is 1-300, l is 1-51, ois 0-10, p is 0-1 when o is less than or equal to one and 1 when o isgreater than 1, wherein R^(1a) or R^(1b) is an insulating resistive tailor both R^(1a) and R^(1b) are insulating resistive tails.

In some implementations of composite polymeric materials of the abovegeneral formula, R^(1a), R^(1b), R^(3a) or R^(3b) may possess at least 7carbon atoms.

In some implementations of composite polymeric materials of the abovegeneral formula, R^(1a), R^(1b), R^(3a), and R^(3b) are insulatingresistive tails are independently selected from the group consisting ofsaturated hydrocarbon, saturated halogenated hydrocarbon, partiallyhalogenated hydrocarbon, aryl chain, and cycloalkyl, and X—RR′R″;wherein X is selected from C, O, N, and S, and R, R′, and R″ areindependently selected from H and C₅₋₅₀, wherein one or more of R, R′,and R″ is C₅₋₅₀.

In some implementations of composite polymeric materials of the abovegeneral formula, the insulating resistive tails may be selectedindependently from the group consisting of non-aromatic carbocycles andnon-aromatic heterocycles.

In some implementations of composite polymeric materials of the abovegeneral formula all insulating resistive tails may be rigid.

In some implementations of composite polymeric materials of the abovegeneral formula, Q₁, Q₂, Q₃, Q₄ and Q₅ are each independently selectedfrom —NO₂, —NH₃ ⁺ and —NRR′R″⁺ (quaternary nitrogen salts) withcounterion Cl⁻ or Br⁻, —CHO (aldehyde), —CRO (keto group), —SO₃H(sulfonic acids), —SO₃R (sulfonates), SO₂NH₂ (sulfonamides), —COOH(carboxylic acid), —COOR (esters, from carboxylic acid side), —COCl(carboxylic acid chlorides), —CONH₂ (amides, from carboxylic acid side),—CF₃, —CCl₃, —CN, —O⁻ (phenoxides) with counter ion Na⁺ or K⁺, —NH₂,—NHR, —NR₂, —OH, OR (ethers), —NHCOR (amides, from amine side), —OCOR(esters, from alcohol side), alkyls, —C₆H₅, vinyls, wherein R and R′ andR″ are radicals selected from the list comprising hydrogen, alkyl(methyl, ethyl, isopropyl, tert-butyl, neopentyl, cyclohexyl etc.),allyl (—CH2-CH═CH2), benzyl (—CH2C6H5) groups, phenyl (+substitutedphenyl) and other aryl (aromatic) groups. In some such implementations,one or more of Q¹, Q², Q³, Q⁴, and Q⁵ may be —NO₂.

In some implementations of composite polymeric materials of the abovegeneral formula, D may be a hydrocarbon chain that is interrupted byheteroatoms at the point of backbone attachment and side chainattachment.

In some implementations of composite polymeric materials of the abovegeneral formula, L₂ may be an azo-bridge or —N═N—, an alkene bridge or—HC═CH—, and alkyne bridge or —C≡C—.

In some implementations of composite polymeric materials of the abovegeneral formula, D may be a hydrocarbon chain interrupted by heteroatomsat the point of backbone attachment and side chain attachment.

In some implementations of composite polymeric materials of the abovegeneral formula, L₂ may be an azo-bridge or —N═N—, an alkene bridge or—HC═CH—, and alkyne bridge or —C≡C—.

Furthermore, aspects of the present disclosure include compositepolymeric materials of the following general formula:

In the foregoing general formula R^(1a) and R^(1b) are independentlyselected from —H, —OH, -Ak, -Ak-X_(l), -OAk, and -OAk-X_(l), Ak isalkyl, X is any halogen, m is 1-300, l is 1-51, and wherein R^(1a) orR^(1b) is an insulating resistive tail or wherein R^(1a) and R^(1b) areboth insulating resistive tails.

In some implementations of composite polymeric materials of the abovegeneral formula, R^(1a) or R^(1b) may possesses at least 7 carbon atoms.

In some implementations of composite polymeric materials of the abovegeneral formula, R^(1a) and R^(1b) may be insulating resistive tails areindependently selected from the group consisting of saturatedhydrocarbon, saturated halogenated hydrocarbon, partially halogenatedhydrocarbon, aryl chain, and cycloalkyl, and X—RR′R″; wherein X isselected from C, O, N, and S, and R, R′, and R″ are independentlyselected from H and C₅₋₅₀, wherein one or more of R, R′, and R″ isC₅₋₅₀. In some such implementations, the insulating resistive tails maybe selected independently from the group consisting of non-aromaticcarbocycles and non-aromatic heterocycles.

In some implementations of composite polymeric materials of the abovegeneral formula, all insulating resistive tails may be rigid.

In some implementations of composite polymeric materials of the abovegeneral formula, the composite polymeric material may have structure 21:

wherein m ranges from 1-300.

Additional aspects of the present disclosure include composite polymericmaterials of the following general formula:

In the foregoing general formula R¹, R^(2a), R^(2b), R^(2c), R^(2d),R^(4a), R^(4b), R^(4c), R^(4d), R^(5a), R^(5b), R^(5c), R^(5d) areindependently selected from —H, —OH, -Ak, -Ak-X_(l), -OAk, or-OAk-X_(l), L₂ is a heteroatom bridge in conjugation with the ringsystem containing R^(2a), R^(2b), R^(2c), R^(2d), Q¹, Q², Q³, Q⁴, Q⁵;wherein R^(2a), R^(2b), R^(2c), R^(2d), Q¹, Q², Q³, Q⁴, Q⁵ are eachindependently selected from —H and any electron withdrawing or electrondonating group, wherein Ak is alkyl, X is any halogen, wherein o is0-10, p is 0-1 when o is less than or equal to one and 1 when o isgreater than 1, wherein R¹ is an insulating resistive tail; wherein Z issubstituted or unsubstituted hydrocarbon cyclic or chain linkage, Y isany hydrocarbon chain which may be interrupted by a hetero atom at thepoint of attachment.

In some implementations of composite polymeric materials of the abovegeneral formula, the composite polymeric material may have structure 22:

wherein m ranges from 1-300.

In some implementations of composite polymeric materials of the abovegeneral formula, R¹ may possess at least 7 carbon atoms.

In some implementations of composite polymeric materials of the abovegeneral formula, R¹ may be an insulating resistive tail selected fromthe group consisting of saturated hydrocarbon, saturated halogenatedhydrocarbon, partially halogenated hydrocarbon, aryl chain, andcycloalkyl, and X—RR′R″; wherein X is selected from C, O, N, and S, andR, R′, and R″ are independently selected from H and C₅₋₅₀, wherein oneor more of R, R′, and R″ is C₅₋₅₀.

In some implementations of composite polymeric materials of the abovegeneral formula, R¹ may be a rigid insulating resistive tail. In somesuch implementations, the rigid insulating resistive tail may beselected from the group consisting of non-aromatic carbocycles andnon-aromatic heterocycles.

In some implementations of composite polymeric materials of the abovegeneral formula, Q₁, Q₂, Q₃, Q₄ and Q₅ may each be independentlyselected from —NO₂, —NH₃ ⁺ and —NRR′R″⁺ (quaternary nitrogen salts) withcounterion Cl⁻ or Br⁻, —CHO (aldehyde), —CRO (keto group), —SO₃H(sulfonic acids), —SO₃R (sulfonates), SO₂NH₂ (sulfonamides), —COOH(carboxylic acid), —COOR (esters, from carboxylic acid side), —COCl(carboxylic acid chlorides), —CONH₂ (amides, from carboxylic acid side),—CF₃, —CCl₃, —CN, —O⁻ (phenoxides) with counter ion Na⁺ or K⁺, —NH₂,—NHR, —NR₂, —OH, OR (ethers), —NHCOR (amides, from amine side), —OCOR(esters, from alcohol side), alkyls, —C₆H₅, vinyls, wherein R and R′ andR″ are radicals selected from the list comprising hydrogen, alkyl(methyl, ethyl, isopropyl, tert-butyl, neopentyl, cyclohexyl etc.),allyl (—CH2-CH═CH2), benzyl (—CH2C6H5) groups, phenyl (+substitutedphenyl) and other aryl (aromatic) groups. In some such implementations,one or more of Q¹, Q², Q³, Q⁴, and Q⁵ may be —NO₂.

The present disclosure provides a metacapacitor comprising two metalelectrodes positioned parallel to each other and which can be rolled orflat and planar and a metadielectric layer between said electrodes andoptionally an insolation layer. The metadielectric layer comprisespolarizable compounds that include composite polymeric materials of anyof the general formulae and implementations discussed above and asdisclosed in further detail below.

Further, the disclosure provides a stacked metacapacitor comprising thestacked structure sequence E(DED)_(m), wherein E are electrodes and Dare metadielectric layers, and m is an integer greater than or equalto 1. In another embodiment, the disclosure provides a stackedmetacapacitor comprising a stack of (EDT)_(m) wherein E is an electrode,D is a metadielectric layer, T is a tape of an electrode and isolationlayer. In still another embodiment, a metacapacitor will have a sequence(E-B1-D-B2-E-B1-D)_(m) wherein E are electrodes, B1 and B2 arerespectively a hole blocking layer and electron blocking layer (or viceversa), and D is a metadielectric layer. In the three aforementionedembodiments, m is an integer greater than or equal to 1.

A metadielectric layer may be a film made from composite polymersreferred to herein as YanLi materials. Such a composite polymericmaterial is characterized by a chemical structure that includes arepeating backbone unit, a polarizable unit, and a resistive tail. Thepolarizable unit must possess a high degree of conjugation. Herein, wedefine “polarizable unit” to mean any multicyclic arrangement whereelectrons are delocalized over the entire portion of the polarizableunit structure via conjugated single and double bonds. Herein,anisometric is defined as the condition of a molecule possessing chargeor partial charge asymmetry along an axis. Possible, non-limiting, formsof this conjugation are polycyclic fused aromatic systems or aconjugated bridge where aromatic systems are connected by alternatingsingle and double bonds.

By way of example, and not by way of limitation, according to aspects ofthe present disclosure, a metadielectric film may include a polymermatrix and at least one material of any of the four general formulaediscussed above or any specific implementations mentioned above ordiscussed further below.

In some embodiments, the metadielectric layer may be comprised of amixture or YanLi materials selected from at least one YanLi material ofthe four general formulae discussed above or a mixture of any specificimplementations mentioned above.

Alternatively, the metadielectric layer maybe comprised of any organiccomposite oligomers, compounds, or polymers as disclosed in U.S. patentapplication Ser. No. 14/710,491 filed May 12, 2015, Ser. No. 15/043,186filed Feb. 12, 2016, Ser. No. 15/043,209 filed Feb. 12, 2016, Ser. No.15/194,224 filed Jun. 27, 2016, Ser. No. 15/043,247 filed Feb. 12, 2016,Ser. No. 15/090,509 filed Apr. 4, 2016, and Ser. No. 15/163,595 filedMay 24, 2016 all of which are entirely incorporated herein.

In some implementations of the above metadielectric film, the polymermatrix may additionally include at least one monomer selected fromacrylate, ester, aramid, repeat units of which YanLi polymers arecomprised.

In some implementations of the above metadielectric film, the film mayinclude a plasticizer.

In some implementations of the above metadielectric film, the film mayinclude a mixture of polyacrylate and polyamide materials.

In some implementations of the above metadielectric film, the film mayhave a relative permittivity greater than or equal to 1000, aresistivity greater than or equal to 10¹⁶ Ohm cm.

According to aspects of the present disclosure, metadielectric films ofthe type described herein may be used in metacapacitors. By way ofexample, and not by way of limitation, a metacapacitor according tocertain aspects of the present disclosure may include a first electrode,a second electrode, and a metadielectric film, e.g., as describedgenerally above or in further detail below, sandwiched between saidfirst and second electrodes.

In some implementations, such a metacapacitor may be characterized by acapacitance that varies non-linearly with voltage.

In some implementations, one or more of the electrodes may be formed ona substrate of flexible tape, wherein the substrate, first and secondelectrodes, and the metadielectric film are coiled such that thesubstrate forms an isolation layer between the first and secondelectrodes, and wherein the substrate is selected from the list ofmaterials according to claim 1 and plastic films.

FIG. 1 illustrates an example of a metacapacitor comprising a firstelectrode 1, a second electrode 2, and a metadielectric layer 3 disposedbetween said first and second electrodes as shown in FIG. 1. Theelectrodes 1 and 2 may be made of a metal, such as copper, zinc, oraluminum or other conductive material such as graphite or carbonnanomaterials and are generally planar in shape.

The electrodes 1, 2 may be flat and planar and positioned parallel toeach other. Alternatively, the electrodes may be planar and parallel,but not necessarily flat, they may be coiled, rolled, bent, folded, orotherwise shaped to form the capacitor. It is also possible for theelectrodes to be non-flat, non-planar, or non-parallel or somecombination of two or more of these. By way of example and not by way oflimitation, a spacing d between the electrodes 1 and 2 may range fromabout 3 nm to about 100 μm. The maximum voltage V_(bd) between theelectrodes 1 and 2 is approximately the product of the breakdown fieldE_(bd) and the electrode spacing d. If E_(bd)=0.1 V/nm and the spacing dbetween the electrodes 1 and 2 is 100 microns (100,000 nm), the maximumvoltage V_(bd) would be 10,000 volts.

Additionally, the metacapacitor may have an insulation layer to insulateelectrodes 1 and 2 from making ohmic contact with each other in coiled,rolled, bent, and folded embodiments. Non-limiting examples of theinsolation layer include metadielectric material, polypropylene (PP),polyethylene terephthalate polyester (PET), polyphenylene sulfide (PPS),polyethylene naphthalate (PEN), polycarbonate (PP), polystyrene (PS),and polytetrafluoroethylene (PTFE).

The electrodes 1 and 2 may have the same shape as each other, the samedimensions, and the same area A. By way of example, and not by way oflimitation, the area A of each electrode 1 and 2 may range from about0.01 m² to about 1000 m². By way of example and not by way of limitationfor rolled capacitors, electrodes up to, e.g., 1000 m long and 1 m wide.

These ranges are non-limiting. Other ranges of the electrode spacing dand area A are within the scope of the aspects of the presentdisclosure.

If the spacing d is small compared to the characteristic lineardimensions of electrodes (e.g., length and/or width), the capacitance Cof the capacitor may be approximated by the formula:C=εε _(o) A/d  (V)where ε_(o) is the permittivity of free space (8.85×10⁻¹²Coulombs²/(Newton·meter²)) and ε is the dielectric constant of thedielectric layer. The energy storage capacity U of the capacitor may beapproximated as:U=½εε_(o) AE _(bd) ² d  (VI)

The energy storage capacity U is determined by the dielectric constantε, the area A, the electrode spacing d, and the breakdown field E_(bd).By appropriate engineering, a capacitor or capacitor bank may bedesigned to have any desired energy storage capacity U. By way ofexample, and not by way of limitation, given the above ranges for thedielectric constant ε, electrode area A, and breakdown field E_(bd) acapacitor in accordance with aspects of the present disclosure may havean energy storage capacity U ranging from about 500 Joules to about2·10¹⁶ Joules.

For a dielectric constant c ranging, e.g., from about 100 to about1,000,000 and constant breakdown field E_(bd) between, e.g., about 0.1and 0.5 V/nm, a capacitor of the type described herein may have aspecific energy capacity per unit mass ranging from about 10 W·h/kg upto about 100,000 W·h/kg, though implementations are not so limited.

Alternatively, in some embodiments, electrodes 1 and 2 may havedifferent shapes from each other with the same or different dimensions,and the same or different areas.

The present disclosure includes metacapacitors that are coiled, e.g., asdepicted in FIGS. 2A, 2B and 3. As shown in FIG. 2A, electrodes 19, 21,e.g., metal electrodes, are formed onto opposite surfaces of ametadielectric layer 17 with margin portions 18, 20 that are free ofmetal located on opposite edges of the metadielectric layer 17. In someembodiments, such a configuration of electrodes 19, 21 andmetadielectric layer 17 form a tape or a multilayered tape. Anelectrically insulating layer 15, e.g., a plastic material is formedover one of the electrodes 21 or a plastic film is overlaid on one ofthe electrodes 21. The electrically insulating layer 15 may includemetadielectric materials or common capacitor insulating materials suchas PET. The metadielectric lay 17 may be formed, e.g., by applying asolution containing YanLi material to the electrode 19 and then dryingthe applied solution to form a solid layer of the YanLi material.

Alternatively, electrodes 19 and 21 may be formed onto opposite surfacesof an insulating layer 15 with margin portions 18, 20 that are free ofelectrode material located on opposite edges of the insulating layer 15.In some embodiments, such a configuration of electrodes 19, 21 andinsulating layer 15 form a tape or a multilayered tape. The electricallyinsulating layer 15 may include metadielectric materials or commoncapacitor insulating materials such as PET. The metadielectric lay 17may be formed, e.g., by applying a solution containing YanLi material tothe electrode 19 and then drying the applied solution to form a solidlayer of the YanLi material.

In some implementations, the applied YanLi material may be a polymerizedsolution of YanLi oligomers which is dried to form a metadielectric. Insome implementations, the YanLi material may be polymerized to form ametadielectric. The thickness of the metadielectric layer may be arelatively uniformly thick layer. The metadielectric layer thickness mayrange from 0.01 μm to 50 μm depending on the desired maximum capacitorvoltage. In general, thicker metadielectric layers are used for highermaximum capacitor voltages. Furthermore, with a given metacapcitor themetadielectric layer thickness may vary due to normal manufacturingprocess variations, e.g., by about 1% to 10% of a nominal thicknessvalue. In this example shown in FIG. 2A the first metal electrode 19 isformed on a portion of a first surface of the metadielectric layer 17with a first margin portion 18 that is free of metal. The secondelectrode 21 is formed on a portion of a second surface of the plasticlayer with a second margin portion 20 located on an opposite edge of themetadielectric layer 17 being free of metal. The multilayered structuredepicted in FIG. 2A may be wound into a coil as shown in FIG. 2B. Theinsulating layer 15 prevents undesired electrical shorts between thefirst and second electrodes after being wound into the coil. By way ofexample and not by way of limitation, the insulating layer 15 mayinclude a metadielectric material, polypropylene (PP), polyethyleneterephthalate polyester (PET), polyphenylene sulfide (PPS), polyethylenenaphthalate (PEN), polycarbonate (PP), polystyrene (PS), orpolytetrafluoroethylene (PTFE).

In the example depicted in FIG. 4, a metacapacitor 22 comprises a firstelectrode 23, a second electrode 25, and a metadielectric material layer24 of the type described herein disposed between said first and secondelectrodes. The electrodes 23 and 25 may be made of a metal, such ascopper, zinc, or aluminum or other conductive material such as graphiteor carbon nanomaterials and are generally planar in shape. In oneimplementation, the electrodes and metadielectric material layer 24 arein the form of long strips of material that are sandwiched together andwound into a coil along with an insulating material 26, e.g., a plasticfilm such as polypropylene or polyester to prevent electrical shortingbetween the electrodes 23 and 25. Alternatively, the insulating materialmay include a metadielectric layer comprised of any composite oligomeror polymer formed therefrom or mixture thereof, as described hereinbelow. In some embodiments, the electrodes may be multilayeredstructures consisting of a conductive layer and any combination of oneor more of layers selected from the list of field planarization layer,surface planarization layer, electron blocking layer, and hole blockinglayer. For examples, a metacapacitor may have a sequence(E-B1-D2-B2-E-B1-D2)_(m) wherein E are electrodes, B1 and B2 arerespectively a hole blocking layer and electron blocking layer (or viceversa), D1 is a metadielectric layer, D2 is selected from ametadielectric layer or a plastic isolation layer (i.e. polypropylene),and m is an integer greater than or equal to 1. Non-limiting examples ofcapacitors and electrodes comprised of field planarization and surfaceplanarization layers are described in U.S. patent application Ser. No.15/368,171 which is herein incorporated by reference in its entirety.

Non-limiting examples of suitable coiled capacitors are described inU.S. patent application Ser. No. 14/752,600 which is herein incorporatedby reference in their entirety. In this aspect, the present inventionprovides a coiled capacitor comprising a coil formed by a flexiblemultilayered tape, and a first terminating electrode (a first contactlayer) and a second terminating electrode (a second contact layer) whichare located on butts of the coil. The flexible multilayered tapecontains the following sequence of layers: first metal layer, a layer ofa plastic, second metal layer, a layer of energy storage material. Thefirst metal layer forms an ohmic contact with the first terminatingelectrode (the first contact layer) and the second metal layer (thesecond contact layer) forms an ohmic contact with the second terminatingelectrode. The layer of energy storage material may be any oligomer orpolymer described herein

FIG. 5 illustrates an example of the chemical structure of a YanLimaterial as a monomer of a polymer, wherein the polarizable unit is adoped chromophore 58, having an electron donor 54, two conjugatedbridges 53, an electron acceptor 52. A tail 51 is covalently bounded tothe electron donor group 54. A composite oligomer forming thepolarizable unit can have more than one electron donor 54, electronacceptor 52, and tail 51. In some embodiments, the composite oligomerforming the polarizable unit has an aromatic ring system in conjugationwith a conjugated bridge. In some embodiments, the aromatic ring systemconsists of fused aromatic rings in conjugation. According to aspects ofthe present disclosure, a composite oligomer may comprise a mixture ofmolecules. YanLi monomers of the type shown in FIG. 5 may be polymerizedto synthesize a YanLi polymer and dried or cured to form a YanLidielectric.

In one embodiment of the present disclosure, the layer's relativepermittivity is greater than or equal to 1000. In another embodiment ofthe present disclosure, the polarization (P) of the metadielectric layercomprises first-order (ε₍₁₎) and second-order (ε₍₂₎) and third order(ε₍₃₎) permittivities according to the following formula:P=ε ₀(ε₁−1)E+ε ₀ε₂ E ²+ε₀ε₃ E ³+ . . .

where P is the polarization of the material, which also can berepresented by the following formula:P=NP _(induced)

where P_(induced) is the induced polarization which can be expressed bythe formula:P _(induced) =αE _(loc) +βE _(loc) ² +γE _(loc) ³+ . . .

where E_(loc) is the localized field and is expressed by the formula:E _(loc) =E+P/(3ε₀)

The real part of the relative permittivity (ε′) as can be seen from theabove equations, also comprises first, second, and third orderpermittivities. Further, permittivity of a capacitor is a function ofapplied voltage and thickness of the capacitor's dielectric (d). Wherevoltage is the DC-voltage which is applied to the metadielectric layer,and d is the layer thickness. In another embodiment of the presentinvention, the metadielectric layer's resistivity is greater than orequal to 10¹⁵ ohm cm. In in some embodiment of the present invention,the metadielectric layer's resistivity is between 10¹⁶ ohm cm and 10²²ohm cm.

Alternatively, in some embodiments the metadielectric layer may becomprised of the aforementioned YanLi materials and the aforementionedoligomers, compounds, polymers, monomers or polymers of the backboneunits of said YanLi materials, one or more plasticizers (phthalates ornon-phthalates), or any combination thereof. Use of non-ionicplasticizers can improve the metadielectric layer's resistivity throughsmoothing out electric field lines. This phenomenon occurs when theplasticizers fill voids and/or assists in supramolecular alignment.Additionally, plasticizers can improve the material's mechanicalproperties by reducing brittleness of the material during and postprocessing.

In one embodiment, the composite polymer comprises more than one type ofresistive tails. In another embodiment, the composite polymer comprisesmore than one type of ordered resistive tails. In yet anotherembodiment, the composite polymer comprises at least one resistive tailor at least one type of ordered resistive tails.

In order that the invention may be more readily understood, reference ismade to the following examples, which are intended to be illustrative ofthe invention, but are not intended to limit the scope.

In one embodiment, a liquid or solid composite polymer is placed betweenthe first and second electrodes. A solid chromophore is, for example,pressed into a pellet and placed between the first electrode and thesecond electrode. The chromophore can be ground into a powder beforepressing.

In another embodiment, at least one type of YanLi polymer or YanLioligomer may be dissolved or suspended in a solvent. The resultantmaterial can be spin coated, extruded via slot die, roll-to-roll coated,or pulled and dried to form a dielectric film.

In another embodiment, a composite oligomer may be dissolved orsuspended in a polymer. This is termed a “guest-host” system where theoligomer is the guest and the polymer is the host. Polymer hostsinclude, but are not limited to, poly(methyl methacrylate), polyimides,polycarbonates and poly(ε-caprolactone). These systems are cross-linkedor non-cross-linked. In some instances, it may be beneficial to usetailless composite oligomers.

In another embodiment, a composite oligomer may be attached to apolymer. This is termed a “side-chain polymer” system. This system hasthe advantages over guest-host systems because high composite oligomerconcentrations are incorporated into the polymer with high order andregularity and without phase separation or concentration gradients. Sidechain polymers include, but are not limited to,poly[4-(2,2-dicyanovinyl)-N-bis(hydroxyethyl)aniline-alt-(4,4′-methylenebis(phenylisocyanate))]urethane,poly[4-(2,2-dicyanovinyl)-N-bis(hydroxyethyl)aniline-alt-(isophoronediisocyanate)]urethane,poly(9H-carbazole-9-ethyl acrylate), poly(9H-carbazole-9-ethylmethacrylate), poly(Disperse Orange 3 acrylamide), poly(Disperse Orange3 methacrylamide), poly(Disperse Red 1 acrylate), poly(Disperse Red 13acrylate), poly(Disperse Red 1 methacrylate), poly(Disperse Red 13methacrylate), poly[(Disperse Red 19)-alt-(1,4-diphenylmethaneurethane)], poly(Disperse Red 19-p-phenylene diacrylate), poly(DisperseYellow 7 acrylate), poly(Disperse Yellow 7 methacrylate), poly[(methylmethacrylate)-co-(9-H-carbazole-9-ethyl acrylate)], poly[(methylmethacrylate)-co-(9-H-carbazole-9-ethyl methacrylate)], poly[methylmethacrylate-co-(Disperse Orange 3 acrylamide)], poly[methylmethacrylate-co-(Disperse Orange 3 methacrylamide)], poly[(methylmethacrylate)-co-(Disperse Red 1 acrylate)], poly[(methylmethacrylate)-co-(Disperse Red 1 methacrylate)], poly[(methylmethacrylate)-co-(Disperse Red 13 acrylate)], poly[(methylmethacrylate)-co-(Disperse Red 13 methacrylate)], poly[methylmethacrylate-co-(Disperse Yellow 7 acrylate)], poly[methylmethacrylate-co-(Disperse Yellow 7 methacrylate)], poly[[(S)-1-(4-nitrophenyl)-2-pyrrolidinemethyl]acrylate],poly[((S)-(−)-1-(4-nitrophenyl)-2-pyrrolidinemethyl)acrylate-co-methylmethacrylate], poly[[((S)-1-(4-nitrophenyl)-2-pyrrolidinemethyl]methacrylate] andpoly[((S)-(−)-1-(4-nitrophenyl)-2-pyrrolidinemethyl)methacrylate-co-methylmethacrylate]. These systems are cross-linked or non-cross-linked.

In another embodiment, composite oligomers may be embedded in matricessuch as oxides, halides, salts and organic glasses. An example of amatrix is inorganic glasses comprising the oxides of aluminum, boron,silicon, titanium, vanadium and zirconium.

According to aspects of the present disclosure, the polymers that makeup a YanLi dielectric may be aligned, partially aligned or unaligned.The composite polymer is preferably aligned for optimal geometricconfiguration of polarizing units as this results in higher capacitancevalues in the capacitor. One method of alignment is to apply a DCelectric field to the composite polymer at a temperature at which thepolarizable units can be oriented. This method is termed “poling.”Poling is generally performed near the glass transition temperature ofpolymeric and glassy systems. One possible method of poling is coronapoling. Other methods of alignment could be roll-to-roll, Meyer bar,dip, slot die, and air knife coating of solutions and liquid crystalsolutions of said side-chain polymers or composite oligomers.

In some instances, the side-chain polymer or composite oligomers mayform liquid crystals in solution or solvent and with or without externalinfluence. Non-limiting examples of liquid crystals include lyotropicand thermotropic liquid crystals. Non-limiting examples of externalinfluences include heat, electric field, mechanical disturbances (e.g.vibration or sonication), and electromagnetic radiation. Said liquidcrystals are supramolecular structures comprised of said side-chainpolymers or composite oligomer in solution or solvent and are orderedand aligned or partially ordered or partially aligned. Such liquidcrystal materials may be coated onto a substrate, e.g., by roll-to-roll,Meyer bar, dip, slot die, or air knife coating in a process thatincludes mechanical ordering of the liquid crystals, and drying of theliquid crystal solution or evaporation of the solvent such that theliquid crystals form a crystalline or semi-crystalline layer or film ofmetadielectric material. Alternatively, such liquid crystal materialsmay be extruded as a film such that the liquid crystals form acrystalline or semi-crystalline film of metadielectric material. In someinstances, extrusion of such liquid crystal materials may be coextrudedas a multilayer film. Such multilayer films may include alternatinglayers of conducting layers and insulating layers, wherein theinsulating layers may be the aforementioned crystalline orsemi-crystalline layer of metadielectric material.

Preferred polymer embodiments are polyester, polyalkylacrylate(preferably methacrylic and acrylic), polyamide, and polyaramid. Thisresistive tail may be attached to the polarizable side chain or may beits own independent side chain interspersed in any pattern or randomassortment with the polarizable side chains or a mixture thereof. Thesespecies can be represented by one of the following formula.

Wherein, each instance of R¹ is independently selected from —H, —OH,-Ak, alkoxy, -OAk-X₀, or -Ak-X_(o), each instance of R² is independentlyselected from —H, —OH, -OAk, or -OAk-X_(o), D is any hydrocarbon chainwhich may be interrupted by hetero atoms at the point of backboneattachment and side chain attachment, L₂ is a heteroatom bridge inconjugation with the ring system of the side chain (e.g. azo-bridge,alkene bridge, and alkyne bridge), each instance of Q is independentlyselected from any electron donating or electron withdrawing group or H,Z is substituted or unsubstituted hydrocarbon cyclic or chain linkage, Yis any hydrocarbon chain which may be interrupted by a hetero atom atthe point of attachment to the side chain, Ak is alkyl, X is anyhalogen, n is 0-150, m is 1-300, o is 1-51, p is 0-10, q is 0-4, and ris 0-4, with the provisio that at least one instance of R¹ must be aresistive tail. Preferred, but not limiting, embodiments of resistivetails include hydrocarbon and halohydrocarbon chains, non-aromatichydrocarbocycles, and non-aromatic heterocycles. In some embodiments, itmay be preferable for the resistive tails to be ridged. In suchembodiments, rigid resistive tails maybe non-aromatic carbocycles ornon-aromatic heterocycles.

The conjugated aromatic ring system may be made further polarizable byadding a variety of functional groups to various cyclic positions of thestructure. Incorporating electron donors and electron acceptors is oneway to enhance the polarizability. Electrophilic groups (electronacceptors) are selected from —NO₂, —NH₃ ⁺ and —NR₃ ⁺ (quaternarynitrogen salts), counterion Cl⁻ or Br⁻, —CHO (aldehyde), —CRO (ketogroup), —SO₃H (sulfonic acids), —SO₃R (sulfonates), SO₂NH₂(sulfonamides), —COOH (carboxylic acid), —COOR (esters, from carboxylicacid side), —COCl (carboxylic acid chlorides), —CONH₂ (amides, fromcarboxylic acid side), —CF₃, —CCl₃, —CN, wherein R is radical selectedfrom the list comprising alkyl (methyl, ethyl, isopropyl, tert-butyl,neopentyl, cyclohexyl etc.), allyl (—CH₂—CH═CH₂), benzyl (—CH₂C₆H₅)groups, phenyl (+substituted phenyl) and other aryl (aromatic) groups.Nucleophilic groups (electron donors) are selected from —O⁻ (phenoxides,like —ONa or —OK), —NH₂, —NHR, —NR₂, —NRR′, —OH, OR (ethers), —NHCOR(amides, from amine side), —OCOR (esters, from alcohol side), alkyls,—C₆H₅, vinyls, wherein R and R′ are radicals independently selected fromthe list comprising alkyl (methyl, ethyl, isopropyl, tert-butyl,neopentyl, cyclohexyl etc.), allyl (—CH2-CH═CH2), benzyl (—CH2C6H5)groups, phenyl (+substituted phenyl) and other aryl (aromatic) groups.Preferred electron donors include, but are not limited to, amino andphosphino groups and combinations thereof. Preferred electron acceptorsinclude, but are not limited to, nitro, carbonyl, oxo, thioxo, sulfonyl,malononitrile, isoxazolone, cyano, dicyano, tricyano, tetracycano,nitrile, dicarbonitrile, tricarbonitrile, thioxodihydropyrimidinedionegroups and combinations thereof. More conjugated bridges include, butare not limited to, 1,2-diphenylethene, 1,2-diphenyldiazene, styrene,hexa-1,3,5-trienylbenzene and 1,4-di(thiophen-2-yl)buta-1,3-diene,alkenes, dienes, trienes, polyenes, diazenes and combinations thereof.

Existence of the electrophilic groups (acceptors) and the nucleophilicgroups (donors) in the aromatic polycyclic conjugated molecule promotesincrease of electronic polarizability of these molecules. Under theinfluence of external electric field electrons are displaced across thepolarizable unit to compensate the electric field. The nucleophilicgroups (donors) and the electrophilic groups (acceptors) add to theelectron density of the polarizable unit, which increases polarizabilityof such molecules and ability to form compensating electric fieldcounter in the presence of an electric field. Thus a distribution ofelectronic density in the molecules is non-uniform. The presence of thepolarizable units leads to increasing of polarization ability of thedisclosed material because of electronic conductivity of the polarizableunits.

Increasing the number of phenyl rings ‘p’ can increase the linearpolarizability (α) and the nonlinear polarizability (β) of theconjugated side chain, as seen in the graphs ‘α vs p’ (depicted in FIG.4A) and ‘β vs p’ (depicted in FIG. 4B), and corresponding Table 1 below,which lists comparative values of α and β for chromophores havingdifferent numbers of phenyl rings. However, increasing the number ofconjugated aromatic rings reduces the side chains solubility. Additionof alkoxy groups to at least one of the side chain rings can improvesolubility of the choromophores while maintaining high non-linearpolarization or slightly improving it. One preferential embodiment isplacement of two methoxy groups on a ring that is separated by oneconjugated bridge and ring from an electron donating group.

TABLE 1 Impact of number of rings on polarizability p α β 2 427 16067 3900 71292 4 1343 121801 5 1699 148208 6 2103 161156

Ionic groups may increase polarization of the disclosed YanLi materialwhen zwitterionic groups are covalently attached to YanLi polymersidechains. The polarizable units can be nonlinearly polarizable and maybe comprised of an aromatic polycyclic conjugated molecule with at leastone dopant group, the polarizable units and are placed into a resistivedielectric envelope formed by resistive substituents. In some instances,the resistive substituents provide solubility of the organic compound ina solvent and act to electrically insulate supramolecular structurescomprised of YanLi polymers from neighboring supramolecular structuresof YanLi polymers. Additionally, said resistive substituents may act toelectrically insulate intra-polymer side chains from one another. Anon-centrosymmetric arrangement of the dopant group(s) can lead to astrong nonlinear response of the compound's electronic polarization inthe presence of an electric field. Additionally, an anisometric moleculeor polarizing unit can lead to a strong nonlinear response of thecompound's electronic polarization in the presence of an electric field.Resistive substituents (e.g. resistive tails described above) increasethe electric strength of these polarizable compounds and breakdownvoltage of the dielectric layers made on their basis.

Specific, but non-limiting embodiments are shown in the following table,wherein co-polymer variants are preferentially alternating more or lessone-to-one, or more-or-less randomly. Di-block co-polymer embodimentsbeing less preferential to alternating monomers one-to-one and random ornear random arrangements.

TABLE 2 Examples of YanLi Polymers

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

Additional specific examples of YanLi polymers include the following:

In many embodiments the composite polymer may include a repeatingbackbone linked to a polarizable unit in the form of one or more azo-dyechromophores. The azo-dye chromophores may consist of phenyl groups inconjugated connection via a conjugated bridge of two heteroatoms (e.g.an azo-bridge), such that there are “n” phenyl groups and “n−1”conjugated bridges where n is an integer between 2 and 16. Side chainsmay be added to the final backbone product or incorporated intoindividual monomers that are then polymerized.

These chromophores impart high polarizability due to delocalization ofelectrons. This polarizability may be enhanced by dopant groups. Thecomposite polymer may further include resistive tails that will provideinsulation within the material. In some embodiments, the resistive tailsare can be substituted or unsubstituted carbon chains (C_(n)X_(2n+1),where “X” represents hydrogen, fluorine, chlorine, or any combinationthereof). In some embodiments, the resistive tails may be rigid fusedpolycyclic aryl groups in order to limit the motion of the side chains,potential stabilizing van der waals interactions between side chainswhile simultaneously making the material more stable by eliminatingvoids. In some embodiments, the resistive tails may be rigid in order tolimit voids within the material. The synthetic scheme for demonstrative,but not exclusive, species are shown below and are expected to beadaptable to the claimed variations.

No technical complications are expected in adapting these syntheses tomonomers bearing both chromophore and resistive tail, as in structures3, 4, 7, 10, 11, 14, 15, and 19 from Table 2.

Examples of suitable chromophores include, but are not limited to,Disperse Red-1, Black Hole Quencher-1, and Black Hole Quencher-2. Inmany of the embodiments it may not be necessary for all monomer units tobear a chromophore, and in some it may be desirable to possess otherside chains or sites within the repeating backbone that impart otherqualities to the material such as stability, ease of purification,flexibility of finished film, etc.

For embodiments where the chromophores are incorporated as side chains,the resistive tails may be added before the side chains are attached toa finished polymer, after side chains have been chemically added to afinished polymer, or incorporated into the polymer during synthesis byincorporation into monomer units.

For embodiments where the chromophore is part of the backbone the tailsmay be attached to the finished composite polymer or incorporated intomonomer units and added during composite synthesis.

Non-limiting examples of suitable tails are alkyl, haloalkyl, cycloakyl,cyclohaloalkyl, and polyether.

Syntheses of eight different YanLi polymers described herein will befurther explained below.

Example 1: Synthesis of Polymer 1

First compound 1-2-((4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)diazenyl)phenyl) diazenyl)phenyl)(ethyl) amino)ethan-1-ol wassynthesized from Fast Black K Salt(2,5-Dimethoxy-4-(4-nitrophenylazo)benzenediazonium chloride zinc doublesalt. Fast Black K Salt (25%, 30 g) was dissolved in 250 mL acetonitrileand 250 mL NaOAc buffer solution (pH=4) and the resulting solution wasstirred for 1 hour and then sonicated for 15 min, followed by vacuumfiltration. The filtrate was dropwise added to a solution of2-(ethyl(phenyl)amino)ethan-1-ol (4.1 g in 65 mL acetonitrile) at 0° C.The resultant solution was stirred at room temperature for 16 hours andthe precipitate was filtered out and washed with mix solvent ofacetonitrile/water (1:1) and dried under vacuum. The product wasobtained as a black powder.

2-((4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)diazenyl)phenyl)diazenyl)phenyl)(ethyl)amino)ethyl methacrylate (Compound 2) is then synthesized fromcompound 1. To the solution of compound 1 (5.0 g) and triethylamine (4.4mL) in 70 mL THF (anhydrous) at 0° C., was dropwise added a solution ofmethacryloyl chloride (3.1 mL) in THF (anhydrous, 10 mL). The resultingsolution was warmed up to room temperature and was stirred overnight atroom temperature. The reaction solution was filtered and THF was used towash the insoluble; the filtrate was concentrated under vacuum anddiluted in dichloromethane. The diluted solution was washed with waterand the solvent was removed under vacuum. The crude product was purifiedwith column chromatography and 3.2 g pure product was isolated as ablack powder.

Polymer 1 was then formed from compound 2 as follows. Compound 2 (2.0g), stearylmethacrylate (1.2 g) and AIBN (160 mg) were dissolved inanhydrous toluene (12 mL) in a sealed flask and the resulting solutionwas heated to 85° C. for 18 hours and then cooled to room temperature.The polymer was obtained by precipitating in isopropanol.

Example 2: Synthesis of Polymer 2

Polymer 2 was synthesized using(E)-2-(ethyl(4-((4-nitrophenyl)diazenyl)phenyl)amino)ethyl methacrylate(compound 3). Compound 3 was synthesized from Disperse Red-1(2-[N-ethyl-4-[(4-nitrophenyl)diazenyl]anilino]ethanol or C₁₆H₁₈N₄O₃)and methacryloyl chloride using preparation procedure of compound 2.

Polymer 2. Polymer 2 was synthesized from compound 3 andstearylmethacrylate using preparation procedure of polymer 1.

Example 3: Synthesis of Polymer 3

Polymer 3 was synthesized using2-((4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)diazenyl)phenyl)diazenyl)phenyl)(ethyl)amino) ethyl nonadecanoate (compound 4), which was synthesizedfrom compound 1 described above: To a solution of compound 1 (0.5 g) andtriethylamine (0.46 mL) in 15 mL THF at 0° C., was dropwise added asolution of stearoyl chloride (1.12 mL) in THF. The resulting solutionwas warmed up to room temperature and was stirred overnight at roomtemperature. The reaction solution was filtered and THF was used to washthe insoluble; the filtrate was concentrated under vacuum and residuewas taken in dichloromethane. The crude product solution was washed withwater and the solvent was removed under vacuum. The crude product waspurified with column chromatography.

Compound 4 was then used to synthesize2-((4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)diazenyl)phenyl)diazenyl)phenyl)(ethyl)amino)ethyl nonadecanoate (compound 5). Specifically, compound 4 (1.0 g)was dissolved in dichloromethane (30 mL) and cooled to −78° C.; BBr₃(0.72 g) was slowly added into the solution. The resulting reactionmixture was slowly warmed to room temperature and was kept at roomtemperature with stirring for 12 hours. Sodium bicarbonate aqueoussolution was injected in the reaction mixture at 0° C. and diluted withdichloromethane. The solution was washed with water and brine, and thenconcentrated under vacuum. The product was purified via flash columnchromatography.

Compound 5 was then used to synthesize compound 6(2-((4-((E)-(2,5-bis(2-aminoethoxy)-4-((E)-(4-nitrophenyl)diazenyl)phenyl)diazenyl)phenyl)(ethyl)amino)ethyl nonadecanoate). Compound 5 (0.73 g), K₂CO₃ (1.38 g)and tert-butyl (2-bromoethyl)carbamate (0.44 g) were added todimethylformamide (DMF) (15 mL), and the resulting mixture was stirredat 65° C. overnight. H₂O (400 mL) was added to the reaction mixture andthe aqueous layer was extracted with EtOAc (200 mL×2). The combinedorganic layer was washed with H₂O (100 mL×2) and brine (50 mL), driedover Na₂SO₄, filtered, and concentrated under reduced pressure. Thecrude product was purified by silica column chromatography. The pureproduct was dissolved in dichloromethane (10 mL) and TFA(trifluoroacetic acid) (3 mL) and the solution was stirred at roomtemperature for 2 hours. Then excess reagent and solvent were removedunder vacuum. The resulting crude product was neutralized by NaHCO₃solution, extracted with CH₂Cl₂ (3×50 mL), dried over MgSO₄ andevaporated. The crude product (compound 6) was purified by silica columnchromatography.

Polymer 3. To the solution of compound 6 (4.1 g) in CH₂Cl₂ (15 mL), wasslowly added adipoyl dichloride (0.9 g) at 0° C. After the addition, thesolution was allowed to warm to room temperature and stir for 2 hours.The resulting solution was concentrated and dropwise added intoisopropanol to precipitate the polymer 3.

Example 4: Synthesis of Polymer 4

The synthesis of polymer 4 begins by synthesizing N-decylaniline(compound 7).

To a solution containing GuHCl (10 mg, 5 mol %) in H₂O (4 mL), was addeddecanal (2 mmol) and aniline (2.2 mmol) and the mixture vigorouslystirred for 15 min at room temperature. After, NaBH₄ (20 mg, 2.1 mmol)was added, the mixture was stirred for additional 10 min. The reactionmixture was extracted with CH₂Cl₂, dried over Na₂SO₄, concentrated undervacuum and the crude mixture was purified by column chromatography onsilica gel to afford the pure products.

2-(Decyl(phenyl)amino)ethan-1-ol (compound 8) is then Synthesized fromCompound 7

To a solution of 7 (470 mg, 2.00 mmol) in toluene (5 ml) was addedtriethylamine (405 mg, 4.00 mmol) and 2-bromoethanol (501 mg, 4.01mmol), and the mixture was refluxed for 2 h. The resulting mixture wasdiluted with saturated NH₄Cl and extracted with ethyl acetate. Theextract was washed with brine, dried over anhydrous MgSO4, filtered, andconcentrated in vacuo. The crude product was purified by silica gelchromatography to give 8.

2-(Decyl(4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)diazenyl)phenyl)diazenyl)phenyl) amino)ethan-1-ol (Compound 9) was then Synthesized from FastBlack K Salt and Compound 8

Fast Black K Salt (25%, 30 g) was dissolved in 250 mL acetonitrile and250 mL NaOAc buffer solution (pH=4) and the resulting solution wasstirred for 1 hour and then sonicated for 15 min, followed by vacuumfiltration. The filtrate was dropwise added to a solution of compound 8(6.8 g in 65 mL acetonitrile) at 0° C. The resultant solution wasstirred at room temperature for 16 hours and the precipitate wasfiltered out and washed with mix solvent of acetonitrile/water (1:1) anddried under vacuum. The product was obtained as a black powder.

2-(decyl(4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)diazenyl)phenyl)diazenyl)phenyl) amino)ethyl Methacrylate (Compound 10)

To the solution of compound 9 (5.0 g) and triethylamine (3.5 mL) in 70mL THF (anhydrous) at 0° C., was dropwise added a solution ofmethacryloyl chloride (2.5 mL) in THF (anhydrous, 10 mL). The resultingsolution was warmed up to room temperature and was stirred overnight atroom temperature. The reaction solution was filtered and THF was used towash the insoluble; the filtrate was concentrated under vacuum anddiluted in dichloromethane. The diluted solution was washed with waterand the solvent was removed under vacuum. The crude product was purifiedwith column chromatography and 3.3 g pure product (compound 10) wasisolated as a black powder.

Poly2-(decyl(4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)diazenyl)phenyl)diazenyl)phenyl) amino)ethyl methacrylate (4) (Polymer 4) was then Synthesizedfrom Compound 10

Compound 10 (2.0 g) and AIBN (40 mg) were dissolved in anhydrous toluene(6 mL) in a sealed flask and the resulting solution was heated to 85° C.for 18 hours and then cooled to room temperature. The polymer (1.4 g)was obtained by precipitating and washing in 2-isopropanol.

Preferred embodiments of the invention will meet one of the followingformulae.

Wherein, each instance of R¹ is independently selected from —H, —OH,-Ak, -OAk, -OAk-X_(o), or -Ak-X_(o), or alkoxy; each instance of R² isindependently selected from H, —OH, -OAk, -OAk-X_(o), or Ak; L₂ is aheteroatom bridge in conjugation with the ring system of the side chain(e.g. azo-bridge or —N═N—, alkene bridge or —HC═CH—, and alkyne or —C≡C—bridge), each instance of Q is independently selected from any electronwithdrawing group or H, Ak is alkyl or branched alkyl or aryl, X is anyhalogen, n is 0-150, m is 1-300, o is 1-51, p is 0-10, with the provisiothat at least one instance of R¹ must be a resistive tail. Preferred,but not limiting, embodiments of resistive tails include hydrocarbon andhalohydrocarbon chains, non-aromatic hydrocarbocycles, and non-aromaticheterocycles. In some embodiments, it may be preferable for theresistive tails to be ridged. In such embodiments, rigid resistive tailsmaybe non-aromatic carbocycles or non-aromatic heterocycles.

Other embodiments of the invention possess a polyester backbone whereresistive tail and Polarizable Unit are each simultaneously side chainsto the same monomer. A sample scheme for polyester embodiments isdepicted below.

Example 5: Synthesis of Polymer 5

This scheme should be widely adaptable to accommodate a variety ofbackbones and polarizable units. Such species would meet the followingformula.

Where each instance of R¹ is independently selected from any alkylgroup, each instance of R² is independently selected from —H, —OH, -OAk,or -OAk-X_(o), L₂ is a heteroatom bridge in conjugation with the ringsystem of the side chain (e.g. azo-bridge or —N═N—, alkene bridge or—HC═CH—, and alkyne or —C≡C— bridge), each instance of Q isindependently selected from any electron donating or electronwithdrawing group, Z is substituted or unsubstituted hydrocarbon cyclicor chain linkage, Y is any hydrocarbon chain which may be interrupted bya hetero atom at the point of attachment, m is 1-300, o is 1-51, p is0-10. Preferred embodiments include m between 60 and 270, and p between1 and 4.

Other embodiments of the invention possess alternative backbones whereresistive tail and Polarizable Unit are each simultaneously side chainsto the same monomer. A sample scheme for polyaramid embodiments isdepicted below.

Example 6: Synthesis of Polymer 6

Synthesis of 12: Add 1,3-dinitrobenzene (11) in a round bottom flaskwith concentrated sulfuric acid (0.5M) with 1.1 equiv. of I₂. Connect toreflux condenser and place reaction vessel in an oil bath heated to 150°C. When the reaction is complete, pour mixture onto ice and filterproduct. Wash solid with sodium bicarbonate until neutralized anddissolve in dichloromethane until dissolved. Wash with aqueous sodiumthiosulfate (10%) solution to remove I₂ and organic solution withmagnesium sulfate before filtering. Remove organic solvent under vacuum,recrystallize, and filter to isolate 12.

Synthesis of 13: Add 12 (1 equiv.), dodecane boronic acid (1.2 equiv),Pd(PPh₃)₂Cl₂ (0.05 equiv), and potassium carbonate (2 equiv.) into areaction vessel. Evacuate and backfill with N₂ three times. Add adegassed mixture of toluene and water (10:1) and heat to 80° C. When thereaction is complete, slowly add 1 M aqueous solution of HCl until theaqueous layer is acidic. Extract with dichloromethane (3×) and dryorganic fractions with MgSO₄ before filtering. Concentrate the crudereaction mixture and filter through celite before recrystallizing.Filter to isolate product 13.

Synthesis of 14: Add 3 (1 equiv) to reaction flask with palladium oncarbon (0.1 equiv). Evacuate and backfill with N₂ before adding ethanol(0.1 M). Fill a balloon and needle with H₂ gas and connect to reactionvessel and heat to 80° C. When the reaction is completed, filter throughcelite making sure the palladium on carbon does not dry. Remove solventunder reduced pressure and recrystallize to purify product 14.

Synthesis of 16: Add 15 (1 equiv.) into a round bottom flask anddissolve in solution of dichloromethane/triethylamine (5:1, 0.1 M). Adda solution of 10 (1.1 equiv, 0.5 M) in dichloromethane to the solutionof 15. When the reaction is complete, wash with 1M aqueous HCl untilacidic and extract with dichloromethane (3 times). Dry organic fractionswith MgSO₄, filter, and concentrate under vacuum. Purify throughcrystallization or SiO₂ column chromatography to isolate 16.

Synthesis of 17: Dissolve 16 (1 equiv.) in dichloromethane (0.1 M) andadd oxalyl chloride (2.1 equiv) with a drop of dimethylformamide ascatalyst. Let reaction stir at room temperature until bubbling stops.Remove solvent under vacuum to isolate 7.

Synthesis of 18: Add 14 (1.0 equiv.) and 17 (1.0 equiv.) to a reactionvessel before adding a mixture of anhydrous tetrahydrofuran andtriethylamine (5:1, 0.1 M). When the reaction is complete, concentrateunder reduced pressure and precipitate to isolate 18.

The scheme for Polymer 6 should be widely adaptable to accommodate avariety of backbones and polarizable units. Such species would meet thefollowing formula.

Where each instance of R¹ is independently selected from any alkyl oralkoxyl group or —H, each instance of R² is independently selected from—H, —OH, -OAk, or -OAk-X_(o), L₂ is a heteroatom bridge in conjugationwith the ring system of the side chain (e.g. azo-bridge or —N═N—, alkenebridge or —HC═CH—, and alkyne or —C≡C— bridge), Q is selected from anyelectron withdrawing group, D is any hydrocarbon chain which may beinterrupted by hetero atoms at the point of backbone attachment and sidechain attachment, m is 1-300, o is 1-51, p is 0-10. Preferredembodiments include m between 60 and 270, and p between 1 and 4.

Examples 7a & 7b: Synthesis of Polymers 7a & 7b

Synthesis of 20: Dissolve 1 (1 equiv.) in a solution of CH₂Cl₂ (0.1 M)and triethyl amine (1 equiv.) and let stir for 10 min. Addtrifluoromethanesulfonic anhydride (1.1 equiv.) slowly and let stir for30 min. Wash reaction mixture with aqueous HCl (1M), extract withdichloromethane, and dry with MgSO₄. Remove solvent to isolate 20.

Synthesis of 21a-21b: Add 4-amino-5-chloro-2-methoxybenzoic acid, alkylpotassium trifluoroborate salt, Pd(OAc)₂ (0.02 equiv.), RuPhos (0.04equiv.), and K₂CO₃ (3 equiv.) to a reaction flask. Evacuate this flaskand backfill with N₂ three times. In a separate flask, combine tolueneand water (0.3 M; 10:1) and sparge with N₂ for 60 minutes. Transfer thissolution mixture to the reaction flask and place this into a preheatedoil bath at 80° C. When the reaction is complete, it should cool to roomtemperature before carefully adding 1M HCl until the aqueous layer hasbeen acidified. Extract this with CH₂Cl₂ and dry the organic fractionswith MgSO₄ before filtering. Remove the organic solvent under reducedpressure and isolate the product by silica gel chromatography to isolate21a or 21b.

The procedure below is adapted from: Molander G A, Sandrock D L.“Potassium trifluoroborate salts as convenient, stable reagents fordifficult alkyl transfers”, Current Opinion in Drug Discovery &Development 2009; 12(6): pages 811-823

Synthesis of 22a-22b: Dissolve 21a or 21b in anhydrous CH₂Cl₂ (0.3M) inan oven dried round bottom flask. Cool this solution to 0° C. in an icebath and add boron tribromide (1M in CH₂Cl₂) slowly. Once addition ofBBr₃ is complete, remove the ice bath and let the reaction mixture towarm up to ambient temperature for 12 hours. When the reaction iscompleted, cool it back to 0° C. and slowly add methanol to quench anyexcess BBr₃ present. Wash this reaction with distilled water and collectthe organic fraction. Dry with MgSO₃, filter, then remove solvent undervacuum. Purify by either recrystallization or silica gel chromatographyto isolate 22a or 22b

Synthesis of 23a-23b: Add either 22a or 22b (1 equiv.) and K₂CO₃ (2equiv) into a round bottom flask and dissolve in solution of anhydrousDIVIF (0.1 M). Dissolve 20 (1.1 equiv, 0.5 M) in DMF and add this to theprevious reaction mixture. Place the reaction mixture in a preheated100° C. oil bath and stir until the reaction is completed. When thereaction is complete, wash with 1M aqueous HCl until acidic and extractwith CH₂Cl₂ (3 times). Dry organic fractions with MgSO₄, filter, andconcentrate under vacuum. Purify through crystallization or SiO₂ columnchromatography to isolate 23a or 23b.

Synthesis of 24a-24b: Dissolve monomers 23b or 23b in toluene (0.4 M) ina round bottom flask equipped with a Dean Stark trap to remove waterformed during the reaction and stir at 110° C. in a preheated oil bath.When the reaction is complete, purify the polymer through precipitationand isolate through filtration or centrifugation.

The scheme for Polymers 7a and 7b should be widely adaptable toaccommodate a variety of backbones and polarizable units. Such specieswould meet the following formula.

Where each instance of R¹ is independently selected from —H or any alkylor alkoxyl group, each instance of R² is independently selected from —H,—OH, -OAk, or -OAk-X_(o), L₂ is a heteroatom bridge in conjugation withthe ring system of the side chain (e.g. azo-bridge or —N═N—, alkenebridge or —HC═CH—, and alkyne or —C≡C— bridge), Q is selected from anyelectron withdrawing group, D is any hydrocarbon chain which may beinterrupted by hetero atoms at the point of backbone attachment and sidechain attachment, m is 1-300, o is 1-51, p is 0-10. Preferredembodiments include m between 60 and 270, and p between 1 and 4.

Synthesis of Polymer 8

Synthesis of 1: Dissolve Fast Black K Salt in acetonitrile and NaOAcbuffer solution (pH=4) and stir the resulting solution for 1 hour,followed by vacuum filtration. Add the filtrate dropwise to a solutionof 2-(ethyl(phenyl)amino)ethan-1-ol at 0-5° C. Stir the solution at roomtemperature for 16 hours before filtering the precipitate and wash witha mixture of acetonitrile/water (1:1) and dried under vacuum.

Synthesis of 20: Dissolve 1 (1 equiv.) in a solution of dichloromethane(0.1 M) and triethyl amine (1 equiv.) and let stir for 10 min. Addtrifluoromethanesulfonic anhydride (1.1 equiv.) slowly and let stir for30 min. Wash reaction mixture with aqueous HCl (1M), extract withdichloromethane, and dry with MgSO₄. Remove solvent to isolate 20.

Synthesis of 25: Add 1-iodo-2-aminobenzene to a round bottom flaskdissolved in dichloromethane (0.1 M) with 1.1 equiv. ofN-bromosuccinimide. Let the reaction stir at room temperature for onehour. When the reaction is complete, wash with aqueous HCl (1 M) andextract with dichloromethane. Dry using MgSO₄, filter, and removeorganic solvent under reduced pressure to isolate 25.

Synthesis of 26: Add 25 (1 equiv.), dodecane boronic acid (1.2 equiv),Pd(PPh₃)₂Cl₂ (0.05 equiv), and potassium carbonate (2 equiv.) into areaction vessel. Evacuate and backfill with N₂ three times. Add adegassed mixture of toluene and water (10:1) and heat to 80° C. When thereaction is complete, slowly add 1 M aqueous solution of HCl until theaqueous layer is acidic. Extract with dichloromethane (3×) and dryorganic fractions with MgSO₄ before filtering. Concentrate the crudereaction mixture and filter through celite before recrystallizing.Filter to isolate product 26.

Synthesis of 27: Add 4-bromosalicylic acid (1 equiv.) into a roundbottom flask with potassium carbonate (1.5 equiv.) and dissolve insolution of dimethylformamide (0.1 M) and heat the reaction to 100° C.for 2 hours. When the reaction is complete, wash with 1M aqueous HCluntil acidic and extract with dichloromethane (3 times). Dry organicfractions with MgSO₄, filter, and concentrate under vacuum. Purifythrough crystallization or SiO₂ column chromatography to isolate 27.

Synthesis of 28: Add 27 (1 equiv.), bispinacolborane (1.5 equiv),Pd(PPh₃)₂Cl₂ (0.05 equiv), and potassium carbonate (2 equiv.) into areaction vessel. Evacuate and backfill with N₂ three times. Add adegassed mixture of toluene and water (10:1) and heat to 80° C. When thereaction is complete, slowly add 1 M aqueous solution of HCl until theaqueous layer is acidic. Extract with dichloromethane (3×) and dryorganic fractions with MgSO₄ before filtering. Concentrate the crudereaction mixture and filter through celite before recrystallizing.Filter to isolate product 28.

Synthesis of 29: Add 28 (1 equiv.), 26 (1 equiv), Pd(PPh₃)₄ (0.05equiv), and potassium carbonate (2 equiv.) into a reaction vessel.Evacuate and backfill with N₂ three times. Add a degassed mixture oftoluene and water (10:1) and heat to 80° C. When the reaction iscomplete, slowly add 1 M aqueous solution of HCl until the aqueous layeris acidic. Extract with dichloromethane (3×) and dry organic fractionswith MgSO₄ before filtering. Concentrate the crude reaction mixture andfilter through celite before recrystallizing. Filter to isolate product29.

Synthesis of 30: Add 29 (1.0 equiv.) to a reaction vessel before addingtoluene and (0.1 M). Connect the reaction vessel to a and dean-starkapparatus and reflux condenser and heat to 150° C. When the reaction iscomplete, concentrate the crude reaction mixture under reduced pressureand precipitate polymer into hexane to isolate 30.

The scheme for Polymer 8 should be widely adaptable to accommodate avariety of backbones and polarizable units. Such species would meet thefollowing formula.

Where each instance of R¹ is independently selected from —H or any alkylor alkoxyl group, each instance of R² is independently selected from —H,—OH, -OAk, or -OAk-X_(o), L₂ is a heteroatom bridge in conjugation withthe ring system of the side chain (e.g. azo-bridge or —N═N—, alkenebridge or —HC═CH—, and alkyne or —C≡C— bridge), Q is selected from anyelectron withdrawing group, D is any hydrocarbon chain which may beinterrupted by hetero atoms at the point of backbone attachment and sidechain attachment, m is 1-300, o is 1-51, p is 0-10. Preferredembodiments include m between about 60 and 270, and p between 1 and 4.

While the above is a complete description of the preferred embodiment ofthe present invention, it is possible to use various alternatives,modifications and equivalents. Therefore, the scope of the presentinvention should be determined not with reference to the abovedescription but should, instead, be determined with reference to theappended claims, along with their full scope of equivalents. Any featuredescribed herein, whether preferred or not, may be combined with anyother feature described herein, whether preferred or not. In the claimsthat follow, the indefinite article “A”, or “An” refers to a quantity ofone or more of the item following the article, except where expresslystated otherwise. As used herein, in a listing of elements in thealternative, the word “or” is used in the logical inclusive sense, e.g.,“X or Y” covers X alone, Y alone, or both X and Y together, except whereexpressly stated otherwise. Two or more elements listed as alternativesmay be combined together. The appended claims are not to be interpretedas including means-plus-function limitations, unless such a limitationis explicitly recited in a given claim using the phrase “means for.”

What is claimed is:
 1. A composite polymeric material having any of thefollowing structures 1 to 19:

wherein n ranges from 0-150 and m ranges from 1-300.